JPS5823847A - Cellulose derivative-containing emuslion composition - Google Patents

Abstract

PURPOSE:The titled composition useful for coating, having improved transparency and surface gloss of a film, and good emulsion stability, obtained by subjecting an ethylenic unsaturated monomer to emulsion polymerization in the presence of a vinyl copolymer modified with a specific cellulose derivative. CONSTITUTION:In the presence of a vinyl copolymer (containing preferably >=50wt% acrylic acid ester, etc.) modified with a cellulose derivative, having an acid value of 3-150, obtained by copolymerizing the cellulose derivative (especially cellulose acetate butyrate) with an ethylenic unsaturated acid (e.g., acrylic acid, etc.) and another ethylenic unsaturated monomer (especially acrylic acid ester, etc.), an ethylenic monomer in a weight ratio of the copolymer to the monomer (1:0.1)-(1:10) is copolymerized in an aqueous medium at 50-200 deg.C in the presence of a radical polymerizing agent by emulsion polymerization. The addition of a polyfunctional unsaturated monomer in an amount to give <=30wt% that of the monomer and not to cause gelation improves emulsion stability, and the surface gloss of a film.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel cellulose derivative-containing emulsion composition, and more specifically, when applied as a coating composition onto a substrate, the coating film has particularly excellent transparency and surface gloss, and The present invention relates to a cellulose-conductor-containing emulsion composition that has poor physical properties such as water resistance and solvent resistance, and emulsion stability.

Conventionally, coatings made of cellulose derivatives have high hardness;
It is used for household and woodworking purposes by mixing with paint resins such as acrylic resins and alkyd resins because it is smooth and feels good on the skin, and has excellent coating properties such as abrasiveness and gasoline resistance. It is widely used as a lacquer and as an automotive refinish paint. However, such mixed-type paints generally require a lot of solvent to maintain paintable viscosity, which is why there is a social problem with modern paints. However, it is not possible to meet the requirements of resource conservation and no pollution, which is a requirement.

Therefore, various attempts have been made to incorporate cellulose derivatives having the above-mentioned properties into water-based emulsion type paints, which are resource-saving and non-polluting paints. For example, JP-A No. 51-28188 describes water, a surfactant, and at least one polymer (cellulose conductor is also cited as an example), and at least one monomer. It is disclosed that the polymers are mixed to form an aqueous dispersion of polymer-monomer particles and then the monomers within the particles are radically polymerized to form an aqueous emulsion composition. However, in this method, when a cellulose derivative is used as a polymer component, the cellulose derivative-monomer emulsification is carried out to form an emulsion unit before polymerization.
That is, it is necessary to conduct the treatment sufficiently until the average particle size is 0.01 to 5 s, and for this purpose, a relatively large amount of surfactant must be used, so that the resulting emulsion composition The film formed is
Since they contain large amounts of surfactant substances, they inevitably suffer from poor water resistance. However, when a cellulose derivative is introduced, the glass transition temperature ('Ty) of the formed polymer increases, and the resulting emulsion composition is generally useless as a coating composition unless a coating aid is added. There are many things. However, if the added water-soluble coalescent agent is used in large amounts, the emulsion system becomes unstable, while if a large amount of water-insoluble coalescent agents is used, the emulsion composition may catch fire. There are disadvantages such as becoming sexually active.

In addition, as a method for improving the above-mentioned drawbacks, the present applicant has previously developed a water-soluble oxidation-curing type compound consisting of at least 1 to 1 radically polymerizable unsaturated monomers and at least one type of cellulose derivative. proposed a method of introducing a cellulose derivative into an emulsion composition by emulsion polymerization in the presence of a resin (see JP-A-56-76422).

The emulsion composition obtained by the above method has a coating surface that is not sticky and has a good texture, and has abrasive properties.
It has excellent properties such as gloss and gasoline resistance and can form a coating film, but it cannot be said to be completely satisfactory in terms of transparency and surface gloss of the coating film when used as a lacquer, and further improvements are needed for practical use. There is room left.

Therefore, as a result of intensive research aimed at improving the above-mentioned drawbacks of cellulose-conductor-containing emulsion compositions, the present inventors found that cellulose derivatives and ethylenically unsaturated monomers were used as dispersion stabilizers. When a certain water-soluble graft copolymer is prepared and an ethylenically unsaturated monomer is emulsion polymerized in the presence of the water-soluble graft copolymer, the performance when formed into a coating film is substantially improved. It is recalled that it is possible to obtain an emulsion composition containing a nine-fiber cast conductor, which solves at once the problems of lack of transparency and surface gloss of the coating film as described above when used as a lacquer, without degrading the quality of the coating. The invention was completed.

Thus, according to the invention, the cellulose-conductor is treated with ethylenically unsaturated acids and other ethylenically unsaturated acids! Emulsion polymerization of at least one ethylenically unsaturated monomer in the presence of a cellulose derivative-modified vinyl copolymer having an acid value of about 3 to about 150 obtained by copolymerizing with a monoacrylic acid A cellulose-conductor-containing emulsion composition obtained by the present invention is provided.

As mentioned above, the cellulose derivative-containing emulsion composition of the present invention comprises a cellulose derivative, an ethylenically unsaturated acid, and another ethylenically unsaturated monomer, and has an acid value of about 3 to about 1.
The essential feature lies in the use of a water-solubilized cellulose derivative-modified vinyl copolymer having a molecular weight within the range of 50 as a dispersion stabilizer.

Therefore, first, this cellulose derivative-modified vinyl copolymer will be explained in more detail.

Cellulose derivative: The cellulose derivative used in the preparation of the above copolymer has cellulose as a paste, and when the obtained emulsion composition is applied to a substrate and dried, the surface of the film formed is sticky. Suitable materials are those that have a good feel to the touch without causing any scratches, have excellent abrasiveness and other physical properties, and have properties that provide a nine-layer coating. Cellulose conductors that can achieve this purpose include:
It is generally used for paints and has a number average molecular weight of about 3,000 to about 300,000, preferably about 5.
Both ester-modified and ether-modified cellulose derivatives within the range of 0.000 to about 150,000 are included.

Representative examples of the former ester-modified cellulose 114 include nitrocellulose, cellulose acetate butyrate, cellulose acetate propionate,
Examples include cellulose acetate phthalate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose phosphate, and cellulose acetate.

Representative examples of the latter ether-modified cellulose derivatives include methylcellulose, ethylcellulose, butylcellulose, benzylcellulose, carboxymethylcellulose, carboxyethylcellulose, aminoethylcellulose, oxyethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose. etc.

Among these cellulose derivatives, cellulose acetate butylene (hereinafter also referred to as CABJ), which is obtained by further butyl etherification of partially acetylated cellulose, is used in the conventional method described above to prepare an emulsion composition. However, according to the present invention, an excellent CAB-containing emulsion composition having the above-mentioned properties can be effectively prepared, and is inherently weather resistant. It is particularly suitable because it is a material with good garlic.

The degree of acetylation of CAB is generally 1 to 34 by weight, preferably 1 to 16 by weight, more preferably 1 to 7 by weight.
Weight: Nibutyl group content is generally 16 to 60, preferably 25 to 60, more preferably 40 to 60.
Multi-leaved tatami: Described in A8TM-D-1343-54T, the viscosity 1 according to the nine foot method is generally o, oos to 5 seconds, preferably o, oos to 3 seconds, more preferably o, oos
- 1 second, specifically, products manufactured by Eastman Kodak Company in the United States, such as product names [The second digit of the former number is the butyl group content (weight 4)] , the third digit of f9 indicates the hydroxyl group content, and the latter number indicates the viscosity (seconds)], and EA13-17
1-2, EAB-381-2゜EAB-531-1, E
Grades such as AB-551-0,2, EAB-551-0,01 are advantageously used.

Ethylenically unsaturated acid: Ethylenically unsaturated acid used to introduce acidic groups into the copolymer obtained by graft copolymerization with the above cellulose derivative is preferably at least one per molecule. It also includes compounds having only 11 radically polymerizable ethylenically unsaturated bonds (c = C<>) and at least one, preferably one or two acid functional groups, such as carboxyl groups, sulfonic groups, etc. and preferably in the following general formula, R1 represents a water atom, a lower alkyl group, or a carboxyl group; R1 represents a hydrogen atom, a lower alkyl group, or a carboxymethyl group; Y represents a carboxyl group, a sulfone group, or a sulfone group; Methyl group (-〇〇, 80.)I
) are suitable. More specifically,
For example, acrylic acid, methacrylic acid, ethylenically unsaturated monocarboxylic acid having 3 to 10 carbon atoms such as croton; ethylenically unsaturated dicarboxylic acid such as maleic acid, fumaric acid, and itacore 611; Examples include ethylenically unsaturated monosulfonic acids such as styrene sulfonic acid.

These ethylenically unsaturated acids can be used alone or in combination of two or more.

Other ethylenically unsaturated monomers: Other ethylenically unsaturated monomers that can be copolymerized with the above-mentioned ethylenically unsaturated acid into the above-mentioned cellulose I conductor include at least 41 ethylenically unsaturated monomers in one molecule. , preferably containing 1 or 2 radically polymerizable ethylenically unsaturated bonds, relatively low molecular weight, usually having 2 to 26 carbon atoms, more preferably 3 to 21 carbon atoms, chain, cyclic or complex. Compounds consisting of the Suikyu type or a combination thereof are included, and specific examples thereof include those exemplified below.

(A) Esters of acrylic acid or methacrylic acid: for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate,
Such as octyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, etc. C1-C11 alkyl or alicyclic ester of acrylic acid or methacrylic acid: monoacrylic acid or monomethacrylic acid of (poly)alkylene glycols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butylene glycol or their monoalkyl ethers Acid ester: glycidyl acrylate 1. Glycidyl methacrylate or an addition condensate of these with C1 to C1, saturated or unsaturated monocarboxylic M (e.g. nistearic acid, linoleic acid, oleic acid, liluic acid):
C1-4 hydroxyalkyl ester of acrylic acid or methacrylic acid such as hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and C1-1. Condensate with saturated or unsaturated monocarboxylic acid.

(B) Two examples of vinyl aromatic compounds λd, styrene, α
-Methylstyrene, vinyltoluene, p-chloroprene, vinylpyridine, etc.

(C) Diolefin compound: For example, butadiene,
C4-I diolefins such as isoprene and chloroprene.

(D) Two examples of monoolefin compounds λ For example, C3~ monoolefins such as ethylene, propylene, butene, etc.

(E) Amides of acrylic acid or methacrylic acid: for example, acrylamide, methacrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, etc.

(F) 7 Acrylonitrile, methacrylate trile.

(G) Carboxylic acid vinyl ester: vinyl acetate, vinyl propionate, Beopamonomer (manufactured by Shell Chemical Co., Ltd.)
etc.

Among these ethylenically unsaturated monomers, particularly preferred in the present invention are esters of acrylic acid or methacrylic acid.

Each of the above ethylenically unsaturated monomers can be used alone or in combinations of 211 or more.

Furthermore, with respect to the ethylenically unsaturated monomer, the total amount of monomers used is 30 times or less, preferably 71 rtl.
In order to produce a stable emulsion, it is suitable to use a polyfunctional unsaturated monomer in the following amount and within a range that does not cause gelation. The term "polyfunctional unsaturated monomer" as used herein refers to one radically polymerizable unsaturated group in the molecule and at least one graft polymerizable unsaturated group that is not directly stabilized by resonance. A monomer containing

Such polyfunctional compounds include, for example, compounds having an allyl group such as esters of acrylic acid or methacrylic acid and allyl alcohol; Esterification products of alicyclic carboxylic acids containing a double bond and hydroxyl group-containing acrylic monomers such as droxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate are included, and such polyfunctional unsaturated If these monomers are used together, graft-reactive unsaturated bonds remain in the obtained cellulose derivative-modified vinyl copolymer, so the ethylenic unsaturation rate and the graft reaction occur during the subsequent emulsion polymerization. The stone can be raised to form a more stable emulsion composition, and the coating obtained from this emulsion composition has particularly good surface gloss.

Among the cellulose derivative-modified vinyl copolymers formed from the above-mentioned components, those particularly preferred in the present invention are:
The water-soluble resin that branches into the fiber enzyme conductor and is graft-polymerized in a good shape contains at least 50 acrylic acid or methacrylic acid esters, and the solubility parameter of the water-soluble resin (hereinafter referred to as SP) is omitted) value is 8.0 to 1O1
5, preferably 8.5 to 10. It is made by adjusting the unsaturated monomers s and the blend so that it falls within the range of O.

Here, SP is generally a condition for solute molecules to be dispersed in solvent molecules in the dissolution phenomenon of a solute-solvent system.
Kl to separate one molecule from each molecular group!
If we express the square root of the cohesive energy per unit volume (cohesive energy density, Cal/Ce) as 100, ΔEt molar heat of vaporization, ■ the molar volume, and 8P as δ, then the cohesive energy is 915 K ” ΔE/V1
] δ=(ΔE/V)T, the unit is (Cal/Ce)"i2.

Sr of the above water-soluble resin ([ is ethylenically unsaturated monomer A
The weight fraction of %B, C... is Ws%Wb.

We..., SP value is expressed as δa1δb, δC..., 4 of the water-soluble resin is the following formula, where the 8P value of the ethylenically unsaturated monomer is Jour
nal of Pa1nt Techriolo
gy Vol.

42, A341 (19) 0) The values listed in sections 76 to 118 were adopted.

Preparation of cellulose-conductor modified vinyl copolymer: an ethylenically unsaturated copolymer consisting of the nine cellulose derivatives described above, at least one ethylenically unsaturated acid and at least one other ethylenically unsaturated monomer. Copolymerization with monomer components can generally be carried out in the presence of a radical polymerization initiator according to a conventional solution polymerization method. The copolymerization ratio of the bicellulose derivative and the above-mentioned ethylenically unsaturated monomer component can vary widely depending on the type of monomer component used*, but in general, the cellulose-conductor: The weight ratio of ethylenically unsaturated monomer components is 1:0.1 to 1:1
0, preferably within the range of 1:0.3 to 1:3. If the amount of the ethylenically unsaturated monomer component is less than the above range, it will be difficult to make the cellulose-derived modified vinyl copolymer water-soluble; There is a tendency for it to become difficult to survive.

In addition, the amount of ethylenically unsaturated acid used as an essential component in the ethylenically unsaturated monomer component to make the obtained cellulose derivative-modified vinyl copolymer water-solubilizable is determined by The theoretical acid value of the derivative-modified vinyl copolymer is about 3 to about 150, preferably about 10 to about 100.
It is blended in an amount that falls within the range of .

Water-miscible organic solvents such as alcohol, cellosolve, calpitol, ether, or diglyme solvents are suitable as solvents that can be used in the above solution polymerization method, and in addition, membrane-forming agents and plasticizers are suitable. etc. 4 can be used. These may be used alone or in combination. In addition, the polymerization temperature is generally about 50 to about 200°C, preferably about 80°C.
Temperatures within the range of from to about 150°C are used.

As the radical polymerization initiator, any initiator that generally generates radicals can be used, but among them,
Organic peroxide types, such as benzoyl peroxide,
Peroxide polymerization initiators such as lauroyl peroxide, digyl peroxide, etc.; and hydroperoxide polymerization initiators such as tcrt-butyl hydroperoxide, cumene hydroperoxide, etc. are preferably used;
Ketone peroxide type and ber ester type polymerization initiators can also be used. Furthermore, instead of using such a radical polymerization initiator, it is also a preferable method to initiate polymerization using ionizing radiation.

In copolymerization reactions using organic peroxides as polymerization initiators as described above, free radicals of organic compounds generated by thermal decomposition of these polymerization initiators generally cause so-called chain transfer to cellulose derivatives. The nine free radicals generated on the cellulose derivative initiate polymerization of the ethylenically unsaturated monomer component, and the ethylenically unsaturated monomer component grows on the cellulose derivative in a branched form; Graft copolymers are believed to be formed and the use of organic peroxides is advantageous. However, since a graft reaction may occur due to chain transfer of monomer radicals, a polymerization initiator that itself does not have a hydrogen abstracting action can also be used.

In the present invention, it is desirable that substantially all of the nine cellulose conductors blended are copolymerized with the ethylenically unsaturated monomer component; however, a small amount of the cellulose derivative may be unreacted. 11. There is no problem even if it is contained in the copolymer.

The cellulose derivative-modified vinyl copolymer thus prepared has a molecular weight of about 3 to about 150, preferably about 10 to about 10
It has a range of theoretical acid numbers of 0.

The fiber cord derivative-modified vinyl copolymer thus obtained is usually neutralized using a known neutralizing agent, preferably volatile amines, ammonia, alkali metal hydroxides, etc., and further treated as necessary. Accordingly, it can be made water-soluble using a water-soluble organic solvent (for example, a cellosolve solvent, an alcohol solvent, etc.), and then used as a dispersion stabilizer according to the present invention.

According to the present invention, at least 1' type of ethylenically unsaturated monomer is emulsion polymerized in the presence of the vinyl copolymer modified with a nine-strand conductor and made water-soluble as described above.

The ethylenically unsaturated monomer to be subjected to the emulsion polymerization is a relatively low molecular weight compound containing at least 41, preferably 1 or 2 radically polymerizable ethylenically unsaturated bonds in the molecule. From among the ethylenically unsaturated acids and other ethylenically unsaturated monomers mentioned in the preparation of the cellulose derivative-modified vinyl copolymer, depending on the physical properties desired for the final engineered carbonate composition, One or more types can be selected as appropriate. Among these, esters of acrylic acid or methacrylic acid, which have good compatibility with the cellulose-conductor modified vinyl copolymer, are preferred, and these monomers account for 50% or more of the total amount of monomer components to be subjected to emulsion polymerization. and the 8P value of the copolymer formed from the unsaturated monomers subjected to emulsion polymerization is 7.5 to 10.
．． 0. Preferably, when the type and amount of unsaturated monomers are adjusted to be in the range of 8.0 to 9.5, the effect of improving the surface gloss and transparency of the coating film based on the improvement of compatibility will be greater.

It is suitable for listening.

As the emulsion polymerization method, a method known per se can be used. For example, in the presence of the above-mentioned dispersion stabilizer, polymerization initiators (e.g., azo compounds, peroxide compounds, diazo compounds, nitrone compounds, sulfides, redox compounds, etc.) or gamma rays may be used as necessary. It is carried out using ionizing radiation or the like, with stirring or in a stationary state, at a temperature above the freezing point and below the boiling point of water, usually at a burial room temperature.

In addition to water, examples of the aqueous medium as the reaction medium for the above polymerization include water,
A mixture of water and a water-miscible organic solvent (for example, alcohol, cellosolve, calpitol, ether, diglyme, glycol solvents, etc.) can be used.

The amount of the ethylenically insoluble monomer used in the emulsion polymerization is generally 0.05 to 10 times the weight of the cellulose-conductor modified vinyl copolymer as the dispersion stabilizer (solid content weight ratio). ), preferably within the range of 0.1 to 3 times the amount.

The cellulose derivative-containing emulsion composition of the present invention generally contains a solid content of 20 to 50% by weight, has excellent stability,
A film formed using the f9ff emulsion composition has excellent transparency and gloss, and can also have high hardness. Furthermore, the film is dense and has excellent properties such as polishability, water resistance, and gasoline resistance.

The emulsion composition of the present invention can be used as a lacquer for household use, woodworking, and automobile repair by adding pigments, antifoaming agents, thickeners, etc. as appropriate.

The invention will now be further explained by way of an example.

In addition, in the examples, "regret" means "weight loss" unless otherwise specified.
shows.

Example 1 200 of cellulose acetate butyrate (Eastma 7 - manufactured by Kodak, trade name: EABsst-0,2) and 2 tons of butyl cellosolve 200F.

4Put in a tube flask and heat to 150℃. After confirming that the contents are completely dissolved, reduce the temperature to 130℃.
Lower it to 1:. In this, allyl methacrylate) 3F,
A mixed solution of methyl methacrylate (67F), inbutyl methacrylate (109F), acrylic acid (221) and benzoyl peroxide (3t) was added dropwise over 40 minutes. After completing the dripping, transfer the contents to 13011: at 3 o'clock.
After cooling, cool down 100'CK. Next, 6°f of methyl methacrylate and 140f of n-butyl methacrylate were added to this, and 60f of water and 30id of 294 ammonia water were added to disperse well. After that, 0.2F of ammonium persulfate was dissolved in 8fK of water to form a solution. Add 9 (3 in l)
Allow the emulsion carbonate to polymerize for a while. In this way, a CAB-containing emulsion composition with a stable solids content of 42.1 mm and a viscosity of 14,000 7 inch was obtained.

The coating film performance is shown in Table 1 below.

Example 2 2T (cellulose acetate petite used in Example 1) 200F and 7'Til Cellosolve 200F are added to a D4 Tulo flask and heated to 150°C. After confirming that the contents were completely dissolved, the temperature was lowered to 130°C, and allyl methacrylate 3F, methyl methacrylate 57F, inbutyl methacrylate) 109
F, acrylic acid 32F and benzoyl peroxide 3
A mixed solution of t was added dropwise over 40 minutes. After dropping, the contents were kept at 130℃ for 3 hours, and then heated to 100℃.
Cooling.

Next, 60f of methyl methacrylate and 140f of n-butyl methacrylate were added to this, and further 600f of water was added.
Add 29 ml of aqueous ammonia and disperse well, add a solution of 0.2 f of ammonium persulfate dissolved in 5 fK of water, and polymerize emulsilane at 90° C. for 3 hours. Thus, the particle size is fine and the solid content is 414'llG with excellent stability.
A CAB-containing emulsion composition with a viscosity of 4,200 yen tip was obtained. The coating film performance is shown in Table IK below.

II Theory Example 3 In Example 2, allyl methacrylate in the unsaturated monomer was prepared using IIK to prepare a CAD-modified vinyl copolymer.
) 3f and methyl methacrylate 572 were replaced with methyl methacrylate 59fK, a solid content of 41.0 and a viscosity of 680 G (a DCAB-containing emulsion composition was obtained in exactly the same manner as in Example 2.

The coating performance will be explained later! IIK is shown.

Example 4 200t% C8-12 of nine cellulose acetate butyrate used in Example 1 (Chisso product; CH.

Add CH, 0H 120 and ethyl cellosolve 60f, and heat to 150°C.
Heat to. After confirming that the contents were completely dissolved, the temperature was lowered to 130°C, and a mixed solution of 1t1 of allyl methacrylate, 1t1 of methyl methacrylate (73F), 94f of inbutyl methacrylate, 32f of acrylic acid, and 3t of benzoyl peroxide was added. Add it dropwise for 40 minutes.

After the addition is complete, the contents are kept at 130°C for 3 hours and then cooled to 100°C.

Next, 60F of methyl methacrylate and 14Of of n-butyl methacrylate were added to this, and further 670F of water was added.
Add 29 and 30 ml of aqueous ammonia and disperse well, add a solution of 0.2 ammonium persulfate dissolved in 5 fK of water, and emulsion polymerize at 90° C. for 3 hours. In this way, a viscous CAD-containing emulsion composition with fine particle size and excellent stability was obtained. When this product was diluted with water to a solid content of 351, the viscosity was 7400 centipoise. The coating film performance is shown in Table 1 below.

Example 5 In Example fl12, the ethylenically unsaturated monomer composition during emulsion polymerization was changed to methyl methacrylate 60f,n
- The same procedure as in Example 2 was repeated except that 100f of butyl methacrylate and 4Of of styrene were used, and the solid content was 39.
A CAB-containing emulsion composition with a viscosity of 6,400 centipoise and a viscosity of 6,400 centipoise was obtained.

The coating film performance is shown in Table 1.

Example 6 In Example 1, the ethylenically unsaturated monomer to be grafted onto CAB was allyl methacrylate 2f1 ethylene acrylate (679% t-butyl methacrylate) 99
F, acrylic acid 321 and benzoyl peroxide 3
A CAB-containing emulsion composition having a solid content of 4171 and a viscosity of 680 centipoise was prepared in the same manner except that t was replaced. The coating film performance is shown in Table 1 below.

Example 7 In Example 1, cellulose acetate butyrate was replaced with BAB381-0.5 (product of Eastman Kodak Company), and the ethylenically unsaturated monomer composition to be graft-polymerized to this was changed to allyl methacrylate 2f, methyl methacrylate. 57f, inbutyl methacrylate) 1
A CkB-containing emulsion composition having a solid content of 42.4 mm and a viscosity of 2000 centivoids was obtained in the same manner as in Example 1, except that a mixed solution of 09 f, acrylic acid 32 F, and benzoyl peroxide 3 f was used. The coating film performance is shown in Table 1 below.

Test method Hardness Painted on a glass plate for 5 hours, 1
After drying for 1, 3 and 7 days, the hardness of the lead basket was measured.

Measures the 20' specular reflection of a coating film painted on a glossy glass plate.

After painting on a water-resistant double-surface treated steel plate and drying for 97 days, place water droplets on the painted surface and observe changes in the paint film after 2 hours.

Visual observation of a coated tube painted on a transparent glass plate.

Stability of emulsion: Visually observe the condition after standing for 30 days.

Claims (1)

[Claims] In the presence of a cellulose-conductor modified vinyl copolymer having an acid value of 1FJ3 to about 150 obtained by copolymerizing a cellulose derivative with an ethylenically unsaturated acid and another ethylenically unsaturated monomer, A cellulose derivative-containing emulsion composition obtained by emulsifying at least one ethylenically unsaturated monomer.